TWI466944B - Impact-modified polycarbonate compositions - Google Patents

Description

Impact modified polycarbonate composition Related patent applications before and after comparison

The present application claims the priority of the German Patent No. 10 2008 062 904, filed on Jan. 23, 2008, the entire disclosure of which is hereby incorporated by reference.

The present invention discloses a polycarbonate composition relating to impact modification, the composition comprising a first graft polymer comprising a ruthenium oxide-acrylate composite rubber as a graft base (wherein the amount of the oxirane rubber is 65 to 95 wt.% (based on the graft base)), and a second graft polymerization comprising a free-state copolymer (ie, a copolymer that is not chemically bonded to rubber) and having a weight average molecular weight of 60,000 to 150,000 g/mole Things. The use of such polycarbonate compositions in the manufacture of molded articles and for molded articles themselves is also disclosed.

US 2002/077417 A1 discloses a flame-protected composition comprising (a) a polycarbonate, (b) a graft polymer having a bismuth-acrylate composite rubber (wherein the ratio of oxime to acrylate) From 99:1 to 1:99), (c) optional fillers (such as talc), (d) phosphates as flame-proofing agents, (e) optional additional additives ( For example, acrylonitrile-butadiene-styrene terpolymer (ABS), styrene-acrylonitrile copolymer (SAN) and anti-drip agent). Revealed to contain The composition of S-2001 is taken as an example. S-2001 is a graft polymer having a graft base of a ruthenium-butyl acrylate composite rubber, which is composed of about 17 wt.% of methyl methacrylate, about 9 wt.% of organic decane and about 74 wt. % butyl acrylate composition. However, US 2002/077417 A1 does not disclose a composition comprising a graft polymer having a ruthenium oxide-acrylate composite rubber as a graft base, wherein the amount of the silicone rubber is from 65 to 95 wt.% (by the grafting) Base)).

JP-A-08-259791 discloses flame protection compositions comprising polycarbonate and a helium oxygen-acrylate rubber having from 30 to 99% of a decane.

JP-A-2000-017136 discloses that the composition comprises polycarbonate, 1 to 40 wt.% of an oligomeric phosphate ester, and a graft polymer having a graft base of a oxime-acrylate rubber, the oxime-acrylate The rubber comprises from 60 to 99 wt.% polyorganosiloxane, optionally polytetrafluoroethylene and optionally talc.

JP-A-2002-069282 discloses the inclusion of polycarbonate, composite rubber (for example SX-005), a composition of an oligomeric phosphate, an oxygenated oil, an optional polytetrafluoroethylene, and an optional additive.

WO-A 00/39210 discloses a graft polymer comprising a polycarbonate, a copolymer, an oligomeric phosphate, a oxirane-acrylate rubber as a grafting group (for example Metablen S-2001). The amount of polyorganosiloxane in the oxy-acrylate rubber ranges from 3 wt.% to 90 wt.%, optional polytetrafluoroethylene, and a reinforcing material such as talc.

EP-A 0 641 827 discloses that the composition comprises an aromatic polycarbonate, a graft polymer of a vinyl monomer grafted onto a diene rubber, a phosphate ester, a polytetrafluoroethylene, an inorganic filler (for example talc powder). ), and a composite rubber of oxime and acrylate rubber.

JP-A 07316409 discloses compositions comprising a polycarbonate, a phosphate ester, a graft polymer having a oxime-acrylate rubber as a graft base, and agglomerated in the oxime-acrylate rubber The amount of the organic siloxane is 1 to 99 wt.% and the amount of the polyalkyl (meth) acrylate rubber is 99 to 1 wt.%.

The foregoing prior art does not mention a composition comprising a second graft polymer having a free-state copolymer (i.e., a copolymer that is not chemically bonded to rubber) having a weight average molecular weight of 60,000 to 150,000.

It is an object of the present invention to provide impact modified polycarbonate molding compositions which have an optimum combination of good elongation at break, good hydrolysis stability and low melt viscosity.

It has thus surprisingly been found that the aforementioned technical and other objects can be achieved, for example, via the following compositions, including

A) 40 to 99 parts by weight, preferably 50 to 90 parts by weight, particularly preferably 60 to 80 parts by weight (in each case, the sum of the parts by weight of the component A+B+C+D) Aromatic polycarbonate and/or aromatic polyester carbonate,

B) 0.5 to 20 parts by weight, preferably 3 to 13 parts by weight, particularly preferably 8 to 13 parts by weight (in each case, the sum of the parts by weight of the component A+B+C+D) The first graft polymer characterized by a graft base oxime-acrylate composite rubber, in a preferred embodiment interpenetrating oxime rubber and poly(meth) acrylate alkyl An epoxy-acrylate composite rubber of an ester rubber, wherein the amount of the neon rubber is 65 to 95 wt.%, preferably 75 to 95 wt.%, specifically 80 to 95 wt.% (based on the graft base) ,

C) 0.5 to 40 parts by weight, preferably 3 to 20 parts by weight, particularly preferably 3 to 7 parts by weight (based on the sum of the parts by weight of the components A+B+C+D) A polymer comprising a free-state copolymer (i.e., a copolymer that is not chemically bonded to rubber) has from 60,000 to 150,000 grams per mole (preferably from 70,000 to 130,000 grams per mole, particularly preferably from 70,000 to 90,000 grams). /mole) the weight average molecular weight,

D) 0 to 20 parts by weight, preferably 0 to 16 parts by weight, particularly preferably 3 to 16 parts by weight (based on the sum of the parts by weight of the component A+B+C+D), selected from One or more polymers of a group consisting of a rubber-free vinyl (co)polymer and a polyalkylene terephthalate,

E) 0 to 50 parts by weight, preferably 0.5 to 25 parts by weight, particularly preferably 0.5 to 5 parts by weight (in each case, the sum of the parts by weight of the component A+B+C+D) Additives,

Wherein the composition is free or substantially free of fire retardant, and all of the parts by weight in the application of the present invention are normalized such that the sum of the parts by weight of the component A+B+C+D in the composition is 100.

The composition may also consist essentially of the listed ingredients. The composition may also consist entirely of the listed ingredients.

The foregoing and other aspects of the invention are disclosed in the following detailed description and examples.

Ingredient A

Suitable aromatic polycarbonates and/or aromatic polyester carbonates according to ingredient A are generally known in the literature and/or can be prepared by methods known in the literature (for aromatic polycarbonates) Preparations, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE -A 3 000 610, DE-A 3 832 396; for the preparation of aromatic polyester carbonates, see, for example, German DE-A 3 077 934).

The preparation of the aromatic polycarbonate can be carried out, for example, via diphenols and carbonates (preferably phosgene), and/or with aromatic dicarboxylic acid dihalides (preferably benzene) Carboxylic acid dihalides) depending on the reaction of the interfacial method, a chain terminator (for example, a monophenol) may be optionally used, and a branching agent having a functionality of three or more than three (for example, a trisphenol or It is carried out by tetraphenols). It is also possible, for example, to prepare via a melt polymerization process in which a diphenol is reacted with diphenyl carbonate.

Preferred phenols for the preparation of aromatic polycarbonates and/or aromatic polyester carbonates (I)

Wherein A is a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylidene, C ₅ - to C ₆ -cycloalkylidene, - O-, -SO-, -CO-, -S-, -SO ₂ -, C ₆ - to C ₁₂ -arylene, which may be further fused to an aromatic ring optionally containing a hetero atom ), or free radical of formula (II) or formula (III)

B is in each case C ₁ - to C ₁₂ -alkyl (preferably methyl), halogen (preferably chlorine and/or bromine), x each independently 0, 1 or 2 , p is 1 or 0, and R ⁵ and R ⁶ may be individually selected for each X ¹ and each independently hydrogen or C ₁ - to C ₆ -alkyl, preferably hydrogen, methyl Or an ethyl group, X ¹ is a carbon and m is an integer of from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X ¹ , R ⁵ and R ^{6 are} both alkyl.

Preferred phenols include hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C ₁ -C ₅ -alkanes, bis-(hydroxyphenyl)-C ₅ -C ₆ - cycloalkanes, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)anthracenes, bis-(hydroxyphenyl)ketones, bis-(hydroxyphenyl)-indoles and alpha, Α-bis-(hydroxyphenyl)-diisopropyl-benzenes, and the like, which are brominated and/or chlorinated derivatives on the ring.

Particularly preferred phenols include 4,4'-dihydroxybiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4- Hydroxyphenyl)-cyclohexane, 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4, 4'-Dihydroxydiphenylhydrazine and its other two- and four-brominated or chlorinated derivatives, such as 2,2-bis-(3-chloro-4-hydroxyphenyl)-propane 2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane or 2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane. 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A) is particularly preferred. The diphenols may be used singly and/or in any admixture. Such diphenols are known in the literature and/or are obtainable according to methods known in the literature.

Chain terminators suitable for the preparation of thermoplastic aromatic polycarbonates include, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long chain alkyl groups. Phenols such as 4-[2-(2,4,4-trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or a monoalkylphenol or a dialkylphenol having a total of 8 to 20 carbon atoms in the alkyl substituent, such as 3,5-di-t-butylphenol, p-isooctylphenol, p-third Octyl phenol, p-dodecyl phenol and 2-(3,5-dimethylheptyl)-phenol and 4-(3,5-dimethylheptyl)-phenol. The amount of the chain terminator used is usually from 0.5 mol% to 10 mol%, based on the molar sum of the diphenols used in the specific case.

The thermoplastic aromatic polycarbonate usually has a weight average molecular weight (M _{w of} 10,000 to 20,000 g/mole, preferably 15,000 to 80,000 g/mole, particularly preferably 24,000 to 32,000 g/mole, for example, Measured by gel permeation chromatography (GPC), ultracentrifugation or scattered light measurement).

The thermoplastic aromatic polycarbonate may be branched by any known method, preferably via 0.05 to 2.0 mol% of a compound having a functionality of three or more than three based on the sum of the diphenols used (for example Branched with a combination of three or more phenolic groups.

The homopolycarbonate and/or copolycarbonate are suitable. For the preparation of the copolycarbonate of component A, it is based on 1 to 25 wt.% (preferably 2.5 to 25 wt.%) of the polyhydroxyloxy end groups based on the total amount of the diphenols used. Diorganomethoxy oxanes are also possible. These are known (see U.S. Patent No. 3,419,634) and/or may be prepared according to methods known in the literature. The preparation of a copolycarbonate comprising a polydiorganomethoxy alkane is described in DE-A 3 334 782.

In addition to the bisphenol A homopolycarbonate, preferred polycarbonates include diphenols having up to 15 mol% of bisphenol A and a molar amount of diphenols (not including the above preferred or special Preferred copolycarbonates, specifically 2,2-bis(3,5-dibromo-4-hydroxyphenyl)-propane.

The aromatic dicarboxylic acid dihalide used for the preparation of the aromatic polyester carbonate is preferably isophthalic acid, p-nonanoic acid, diphenyl ether 4,4'-dicarboxylic acid and naphthalene-2,6- Dicarboxylic acid diacid dichlorides. Mixtures having isophthalic acid and p-citric acid diacid dichloride in a ratio of 1:20 to 20:1 are particularly preferred.

In the preparation of the polyestercarbonate, a carbonic acid halide (preferably phosgene) may be additionally used as the difunctional acid derivative.

For the preparation of aromatic polyester carbonates, suitable chain terminators, in addition to the monophenols already mentioned, include the chlorocarbonates and the acid chlorides of the aromatic monocarboxylic acids, etc. It may be optionally substituted via a C ₁ - to C ₂₂ -alkyl group or via a halogen atom and an aliphatic C ₂ - to C ₂₂ -monocarboxylic acid chloride.

The amount of chain terminator is preferably from 0.1 to 10 mol% in each case, in the case of a phenolic chain terminator, in moles of diphenol, and in the monocarboxylic acid chloride chain terminator. In the case of the number of moles of dicarboxylic acid dichloride.

The aromatic polyester carbonate may also optionally contain aromatic hydroxycarboxylic acids in combination therein.

In a known manner, the aromatic polyester carbonates can be linear and branched (see DE-A 2 940 024 and DE-A 3 007 934 for this point).

It is possible to use, as a branching agent, for example, a carboxylic acid chloride having a functionality of three or more, in an amount of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichloride used), such as 1 , 3,5-trisic acid trichloride, cyanuric acid trichloride, 3,3'-diphenyl ketone-tetracarboxylic acid tetrachloride, 4,4'- Diphenyl ketone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, or a phenol having three or more functionalities, such as phloroglucinol, 4,6-dimethyl-2, in an amount of 0.01 to 1.0 mol% (based on the diphenol used) 4,6-tris-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4,6-tris-(4-hydroxyphenyl)-heptane, 1,3 , 5-tris-(4-hydroxyphenyl)-benzene, 1,1,1-tris-(4-hydroxyphenyl)-ethane, tris-(4-hydroxyphenyl)-phenylmethane, 2, 2-bis[4,4-bis(4-hydroxy-phenyl)-cyclohexyl]-propane, 2,4-bis(4-hydroxyphenyl-isopropyl)-phenol, tetra-(4-hydroxybenzene) Methane, 2,6-bis(2-hydroxy-5'-methyl-benzyl)-4-methyl-phenol, 2-(4-hydroxyl 2-(2,4-dihydroxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl])-phenoxy)-methane, 1,4-bis[4 ',4"-Dihydroxytriphenyl)-methyl]-benzene. Phenolic branching agents can be placed in a container together with diphenols; acid chloride branching agents can be introduced together with acid dichlorides .

In the thermoplastic aromatic polyester carbonate, the content of the carbonate structural unit can be varied as needed. The content of the carbonate group is preferably up to 100 mol%, specifically up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of the ester group and the carbonate group. The esters and carbonates contained in the aromatic polyester carbonate may be present in the form of blocks or randomly distributed in the polycondensation product.

The relative solution viscosity (η _rel ) of the aromatic polycarbonate and the polyester carbonate is advantageously in the range of 1.18 to 1.4, preferably 1.20 to 1.32 (for 0.5 gram of polycarbonate or polyester carbonate at 100) The solution in milliliters of dichloromethane solution is measured at 25 ° C)

The thermoplastic aromatic polycarbonates and polyester carbonates can be used individually and/or in any optional mixture.

Ingredient B

Ingredient B preferably comprises one or more of the following graft polymers

B.1 5 to 95 wt.%, preferably 10 to 90 wt.%, specifically 10 to 50 wt.% of a vinyl monomer grafted to one or more of the following

B.2 95 to 5 wt.%, preferably 90 to 10 wt.%, specifically 50 to 90 wt.% of one or more of the oxime-acrylate composite rubber as a graft base, the oxime-acrylic acid Ester composite rubber contains

B.2.1 65 to 95 wt.%, preferably 75 to 95 wt.%, specifically 80 to 95 wt.% of the silicone rubber and

B.2.2 5 to 35 wt.%, preferably 5 to 25 wt.%, specifically 5 to 20 wt.% of the polyalkyl (meth) acrylate rubber,

In one preferred embodiment, the two mentioned rubber components B.2.1 and B.2.2 are interpenetrated in the composite rubber such that they are substantially inseparable from each other.

The graft copolymer B can be prepared via free radical polymerization, for example, via emulsification, suspension, solution or bulk polymerization, preferably via emulsion polymerization.

In a preferred embodiment, the graft polymer has a core-shell structure having a rubber core and an ethylene polymer shell.

Suitable monomers B.1 include vinyl type monomers such as ethylene type aromatic compounds and/or cyclically substituted vinyl type aromatic compounds (such as styrene, α-methylstyrene, p-methyl) Styrene, p-chlorostyrene), (C ₁ -C ₈ )-alkyl methacrylates (such as methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, A Allyl acrylate), acrylic acid (C ₁ -C ₈ )-alkyl esters (such as methyl acrylate, ethyl acrylate, n-butyl acrylate, tributyl acrylate), organic acids (such as acrylic acid, methyl Acrylic acid and/or vinyl type cyanides (such as acrylonitrile and methacrylonitrile) and/or derivatives of unsaturated carboxylic acids (such as anhydrides and quinones) (such as maleic anhydride and N-phenyl maleimide). These vinyl monomers may be used singly and/or as a mixture of at least two monomers.

Preferably, monomer B.1 is selected from at least one of the group consisting of monomeric styrene, alpha-methylstyrene, methyl methacrylate, n-butyl acrylate, and acrylonitrile. It is particularly preferred to use a mixture of styrene and acrylonitrile or methyl methacrylate as monomer B.1. In a particularly preferred embodiment, methyl methacrylate is used as monomer B.1.

The glass transition temperature of the graft base B.2 is usually <10 ° C, preferably <0 ° C, particularly preferably < -20 ° C. The graft base B.2 usually has an average particle size (d ₅₀ value) of from 0.05 to 10 μm, preferably from 0.06 to 1 μm, particularly preferably from 0.08 to 0.5 μm, specifically from 0.08 to 0.25 μm.

The average particle size d ₅₀ is 50% by weight of particles each in each case above or below its value. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid-Z. und Z. Polymere 250 (1972), 782-796).

Suitable graft bases B.2 include oxime-acrylate rubbers having a high bismuth oxygen content. These oxirane-acrylate rubbers have a graft-active position and comprise 65 to 95 wt.% (preferably 75 to 95 wt.%, specifically 80 to 95 wt.%) of a silicone rubber component and 5 a composite rubber of a polyalkyl (meth) acrylate rubber component of 35 wt.% (preferably 5 to 25 wt.%, specifically 5 to 20 wt.%), the two mentioned rubber components, In a preferred embodiment, the composite rubber is infiltrated into each other in such a manner that they are substantially inseparable from each other.

Oxygen-acrylate rubbers are known and are described in, for example, US 5,807,914, EP 430,134 and US 4,888,388.

Suitable oxime rubber components of the oxime-acrylate rubber are oxime rubbers having a graft-active position, and the preparation methods thereof are, for example, US 2,891,920, US 3,294,725, DE-OS 3 631 540, EP 249964, It is described in EP 430 134 and US 4,888,388.

The oxirane rubber is preferably prepared via emulsion polymerization using a decyl alkoxide monomer structural unit, a crosslinking agent or a branching agent (IV) and an optional grafting agent (V).

It is possible to use, as a unit of a structural unit of a decyloxy group, for example and preferably, dimethyl methoxy oxane or a cyclic organic oxane having at least a 3-ring structure (preferably a 3 to 6 ring structure). For example, and preferably, hexamethylcyclotrioxane, octamethylcyclotetraoxane, decamethylcyclopentaoxane, dodecamethylcyclohexaoxane, trimethyl- Triphenyl-cyclotrioxane, tetramethyl-tetraphenyl-cyclotetraoxane, octaphenylcyclotetraoxane. The organomethoxyalkane monomer can be used singly and/or as a mixture of two or more monomers. The silicone rubber preferably contains not less than 50% by weight and particularly preferably not less than 60% by weight of the organic oxirane based on the total weight of the siloxane rubber component.

As the crosslinking agent or branching agent (IV), a crosslinking agent based on a decane having a functionality of 3 or 4 (particularly preferably 4) is preferably used. Preferred examples which may be mentioned include trimethoxymethyl decane, triethoxyphenyl decane, tetramethoxy decane, tetraethoxy decane, tetra-n-propoxy decane and tetrabutoxy decane. The crosslinking agent can be used singly and/or in a mixture of two or more. Tetraethoxydecane is particularly preferred.

The crosslinking agent can be usually used in an amount ranging from 0.1 to 40% by weight based on the total weight of the silicone rubber component. The amount of the crosslinking agent is preferably selected such that the silicone rubber has a moisture content of from 3 to 30, preferably from 3 to 25 and particularly preferably from 3 to 15, as measured in toluene. The degree of moisture is defined as the weight ratio of the amount of toluene absorbed by the silicone rubber when the silicone rubber is saturated with toluene at 25 ° C and the amount of the silicone rubber is in a dry state. The measurement of the degree of moisture is described in detail in EP249964.

If the degree of moisture is less than 3, that is, if the content of the crosslinking agent is too high, the silicone rubber may not have sufficient rubber elasticity. If the swelling index is greater than 30, the silicone rubber may not form a domain structure in the matrix polymer and thus may not significantly improve the impact strength; this effect is therefore potentially similar to simply polydimethylation. The effect of the addition of oxane.

In some cases, the tetrafunctional branching agent is preferred over the trifunctional branching agent because it is easier to control within the above advantageous limits.

Suitable grafting agents (V) include compounds having the structural ability to form the following formula:

CH ₂ =C(R ² )-COO-(CH ₂ ) _p -SiR ¹ _n O _(3-n)/2 (V-1)

CH ₂ =CH-SiR ¹ _n O _(3-n)/2 (V-2)

HS-(CH ₂ ) _p -SiR ¹ _n O _(3-n)/2 (V-3)

Wherein R ¹ represents C ₁ -C ₄ -alkyl (preferably methyl, ethyl or propyl), or phenyl, R ² represents hydrogen or methyl, n represents 0, 1 or 2 and p represents 1 An integer of up to 6.

The acryloyl- or methacryl-yl-oxydecane is particularly suitable for forming the above-mentioned structure (V-1) and having a high grafting efficiency. Thereby, the effective formation of the graft chain is generally ensured, and then the impact strength of the resulting resin composition is generally promoted.

Preferred examples which may be mentioned include: β-methacryloxycarbonyl-ethyldimethoxymethyl-decane, γ-methylpropenyloxy-propylmethoxydimethyl-decane , γ-methacryloxycarbonyl-propyldimethoxymethyl-decane, γ-methylpropenyloxy-propyltrimethoxy-decane, γ-methylpropenyloxy- Propyl ethoxydiethyl-decane, γ-methylpropenyloxy-propyldiethoxymethyl-decane, δ-methylpropenyl-oxy-butyldiethoxymethyl a mixture of benzyl or decane or the like.

It is preferred to use from 0 to 20 wt.% of the grafting agent based on the total weight of the silicone rubber.

Suitable polyalkyl (meth) acrylate rubber components of oxime-acrylate rubber may be derived from alkyl methacrylates and/or alkyl acrylates, a crosslinking agent (VI) and a graft Preparation of agent (VII). Examples of preferred alkyl methacrylates and/or alkyl acrylates include C ₁ - to C ₈ -alkyl esters such as methyl ester, ethyl ester, n-butyl ester, tert-butyl ester, and n-propyl ester. Ester, n-hexyl ester, n-octyl ester, n-dodecyl ester and 2-ethylhexyl ester; haloalkyl esters, preferably halo-C ₁ -C ₈ -alkyl esters, such as chloroethyl acrylate Esters, and mixtures of such monomers. N-butyl acrylate is particularly preferred.

A crosslinking agent (VI) as a polyalkyl (meth) acrylate rubber component for a oxy-acrylic rubber may be used, for example, a monomer having more than one polymerizable double bond. Preferred examples of the crosslinking monomer are an unsaturated monocarboxylic acid having 3 to 8 carbon atoms and an unsaturated monohydric alcohol having 3 to 12 carbon atoms, or 2 to 4 OH groups and 2 to 20 Esters of saturated polyols of carbon atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butanediol Acrylate. The crosslinking agent can be used singly and/or as a mixture of at least two crosslinking agents.

Examples of preferred grafting agents (VII) include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate or mixtures thereof. Allyl methacrylate can also be used as the crosslinking agent (VI). The grafting agent can be used singly and/or as a mixture of at least two grafting agents.

The amount of the crosslinking agent (VI) and the grafting agent (VII) is 0.1 to 20% by weight based on the total weight of the polyoxyalkyl (meth) acrylate rubber component of the oxime acrylate rubber.

Theoretically, the oxirane-acrylate rubber can be polymerized as desired in the first polymerization stage via the oxirane rubber and the polymerization of the acrylate rubber component in the second polymerization stage, or in the reverse order. preparation.

In a preferred embodiment, the helium oxide-acrylate rubber can be prepared via a silicone rubber first prepared in the form of an aqueous rubber. The oxime rubber can be prepared by emulsion polymerization, as described in US Pat. No. 2,891,920 and US Pat. No. 3,294,725. For this purpose, in the presence of an emulsifier (preferably a sulfonic acid-based emulsifier such as an alkylbenzene sulfonic acid or an alkyl sulfonic acid), it will comprise an organic oxane, a crosslinking agent and A mixture of optional grafting agents is mixed with water in a sheared manner (e.g., by a homogenizer) which is completely polymerized to produce a silicone rubber. An alkylbenzene sulfonic acid is particularly suitable because it acts not only as an emulsifier but also as a polymerization initiator. In this case, the combination of a sulfonic acid with a metal salt of an alkylbenzenesulfonic acid or a metal salt of an alkylsulfonic acid is advantageous because the polymer is stabilized during subsequent graft polymerization. The reason for this.

After the polymerization, the reaction is terminated by the addition of an aqueous alkaline solution to neutralize the reaction mixture, for example via the addition of sodium hydroxide, potassium hydroxide and/or aqueous sodium carbonate.

In the preferred embodiment, the rubber is then reinforced with the alkyl methacrylate and/or alkyl acrylate, crosslinking agent (VI) and grafting agent (VII) used, and A polymerization. Preferred are emulsion polymerizations initiated by free radicals, for example via peroxides, azo compounds or redox initiators. Particularly preferred is the use of a redox initiator system, particularly a hydroxy group prepared by combining ferrous sulfate, disodium ethylenediamine tetraacetate, ronglite, and hydrogen peroxide. Sulfate starter system.

The grafting agent (V) used in the preparation of the silicone rubber generally has an effect of covalently bonding a polyalkyl (meth) acrylate rubber component to a silicone rubber component. In the polymerization, the two rubbers penetrate each other and thus form a composite rubber, which can no longer be easily separated into components of the silicone rubber component and the polyalkyl (meth)acrylate rubber component after the polymerization. .

For the preparation of the oxime-acrylate graft rubber B, the monomer B.1 was grafted onto the rubber base B.2.

Polymerization methods as described in EP 249 964, EP 430 134 and US Pat. No. 4,888,388 can be used.

For example, graft polymerization can be suitably carried out according to the following polymerization method. In a single-stage or multi-stage emulsion polymerization initiated by a free radical, the suitable vinylic monomer B.1 is polymerized on a graft base which is present in the form of an aqueous rubber. The grafting efficiency should thereby be as high as possible and preferably greater than or equal to 10%. The grafting efficiency is significantly dependent on the grafting agent (V) or (VII) used. After the polymerization of the oxime-acrylate graft rubber, the aqueous rubber is added, for example, to hot water which has previously dissolved metal salts such as calcium chloride or magnesium sulfate. The oxime-acrylate graft rubber is thereby agglomerated and subsequently separated and optionally washed in a preferred embodiment.

Ingredient C

Component C is one or more of the following graft polymers

C.1) 5 to 95 wt.%, preferably 30 to 90 wt.%, particularly preferably 80 to 90 wt.%, specifically 85 to 90 wt.%, of the following mixture, based on the component C

C.1.1) 65 to 85 wt.%, preferably 70 to 80 wt.%, based on C.1, of at least one of ethylene-type aromatic compounds (e.g., styrene, α-methylstyrene), in the ring Upper substituted vinyl type aromatic compounds (for example, p-methylstyrene, p-chlorostyrene) and methacrylic acid (C ₁ -C ₈ )-alkyl esters (such as methyl methacrylate, A Monomer selected from the group consisting of ethyl acrylate), and

C.1.2) 15 to 35 wt.%, preferably 20 to 30 wt.%, based on C.1, of at least one of vinyl cyanide species (e.g., unsaturated nitriles such as acrylonitrile and methacrylonitrile) , (C ₁ -C ₈ )-alkyl (meth)acrylates (such as methyl methacrylate, n-butyl acrylate, tributyl acrylate) and derivatives of unsaturated carboxylic acids (such as anhydrides) Monomer selected from the group consisting of quinone imines (eg, maleic anhydride and N-phenyl-maleimidoimine)

Grafted on the following

C. 2) 95 to 5 wt.%, preferably 70 to 10 wt.%, particularly preferably 20 to 10 wt.%, in particular at least one of 15 to 10 wt.% has <0 ° C (preferred It is a graft base of a glass transition temperature of < -20 ° C. The graft base C.2) usually has a 0.05 to 10 μm (preferably 0.1 to 5 μm, particularly preferably 0.15 to 2 μm, specific The average particle size (d ₅₀ value) of 0.5 to 1.5 μm.

The average particle size d ₅₀ is 50% by weight of particles each in each case above or below its value. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

Preferably, the monomer C.1.1 is selected from at least one of monomeric styrene, α-methylstyrene and methyl methacrylate; preferably, the monomer C.1.2 is selected from the monomers acrylonitrile, cis. At least one of butylene dianhydride and methyl methacrylate.

Particularly preferred monomers include C.1.1 styrene and C.1.2 acrylonitrile.

In addition to the oxime-acrylate (composite) rubber, a suitable graft base C.2 for the graft polymer C, for example, a diene rubber, a diene-vinyl block copolymer rubber, an ethylene-propylene (Diene) monomer (EP (D) M) rubber (ie rubber based on ethylene / propylene and optional diene), acrylate, polyurethane, oxime, chloropyride ( Chloroprene) and ethylene/vinyl acetate rubbers, and mixtures of such rubbers.

Preferred graft bases C.2 include butadiene rubber, isoprene rubber, copolymers of diene rubber, butadiene rubber and other copolymerizable monomers (eg according to C.1.1 and C) .1.2) a copolymer selected from the group consisting of copolymers and isoprene rubbers and at least one diene rubber selected from the group consisting of copolymers of copolymers (for example, according to C.1.1 and C.1.2) Rubber class. Pure polybutadiene rubber and styrene-butadiene block copolymer rubber are particularly preferred.

The graft polymer has a gel content of at least 15 wt.%, preferably at least 20 wt.%, particularly preferably from 20 to 40 wt.% (measured in acetone). The gel content of the graft polymer is determined at 25 ° C in a suitable solvent (M. Hoffmann, H. Kr Mer, R. Kuhn, Polymeranalytik Iund II, Georg Thieme-Verlag, Stuttgart 1977).

Particularly preferred polymer C is, for example, an acrylonitrile-butadiene-styrene (ABS) polymer (emulsified, mass, solution and suspension polymerization ABS) prepared by radical polymerization, for example, In DE-A 2 035 390 (=US-PS 3 644 574) or in DE-A 2 248 242 (=GB-PS 1 409 275) or in Ullmanns Enzyklop Die der Technischen Chemie, Vol. 19 (1980), p. 280 ff. Particularly preferred polymer C is an ABS prepared by bulk, solution or suspension polymerization.

The graft polymer C comprises a free-state copolymer of C.1.1 and C.1.2, i.e., a copolymer that is not chemically bonded to a rubber-based, which is distinguished by the fact that it can be dissolved in a suitable solvent such as acetone.

Component C preferably comprises a free-form copolymer of C.1.1 and C.1.2 having a weight average molecular weight (Mw) of from 60,000 to 150,000 g/mole (preferably from 70,000 to 130,000 g/mole, particularly Preferably, it is 70,000 to 90,000 g/mole, as determined by gel permeation chromatography.

Ingredient D

Component D preferably comprises one or more thermoplastic vinyl (co)polymers D.1 and/or polyalkylene terephthalates D.2.

Suitable vinyl (co)polymers D.1 include from aromatic aromatic compounds, vinyl cyanides (unsaturated nitriles), (meth)acrylic (C ₁ -C ₈ )-alkyl A polymer of at least one monomer of a group of esters, unsaturated carboxylic acids, and derivatives of unsaturated carboxylic acids such as anhydrides and quinones. Particularly suitable for the following (co)polymers

D.1.1 50 to 99 parts by weight, preferably 60 to 80 parts by weight, specifically 70 to 80 parts by weight of the vinyl type aromatic compound and/or the ring-substituted vinyl type aromatic compound ( Such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and/or (C ₁ -C ₈ )-alkyl (meth)acrylates (such as methacrylic acid) Ester, ethyl methacrylate), and

D.1.2 1 to 50 parts by weight, preferably 20 to 40 parts by weight, specifically 20 to 30 parts by weight of a vinyl type cyanide (unsaturated nitrile) (such as acrylonitrile and methacrylonitrile) And/or (C ₁ -C ₈ )-alkyl (meth)acrylates (such as methyl methacrylate, n-butyl acrylate, tributyl acrylate), and/or unsaturated carboxylic acids ( Derivatives such as maleic acid and/or unsaturated carboxylic acids such as anhydrides and quinazones (e.g., maleic anhydride and N-phenyl maleimide).

The vinyl (co)polymer class D.1 is generally similar to a resin, thermoplastic and rubber-free. Particularly preferred are copolymers of D.1.1 styrene and D.1.2 acrylonitrile.

The polymer(s) according to D.1 are known and can be prepared, for example, via free radical polymerization, in particular via emulsification, suspension, solution or bulk polymerization. The (co)polymers preferably have an average molecular weight Mw of from 15,000 to 200,000 g/mole, particularly preferably from 60,000 to 150,000 g/mole, specifically 70,000 to 130,000 g/mole. Average, determined by light scattering or sedimentation).

The polyalkylene terephthalate of component D.2 is preferably an aromatic dicarboxylic acid or a reactive derivative thereof (such as a dimethyl ester or an anhydride) and an aliphatic or cycloaliphatic group. Or a reaction product of an aryl aliphatic diol, and a mixture of such reaction products.

Preferably, the polyalkylene terephthalate ester comprises, based on the dicarboxylic acid component, at least 80 wt.% (preferably at least 90 wt.%) of the perrhenic acid free radical and based on the diol component. At least 80 wt.% (preferably at least 90 wt.%) of ethylene glycol and/or 1,4-butanediol free radicals.

In addition to the inclusion of a decanoic acid free radical, preferred polyalkylene tert-butyl esters may comprise, for example, up to 20 mol% (preferably up to 10 mol%) having from 8 to 14 carbon atoms. Free radicals of other aromatic or cycloaliphatic dicarboxylic acids or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as citric acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4' a free radical of biphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, sebacic acid or cyclohexane diacetic acid.

In addition to comprising ethylene glycol or 1,3-propanediol or 1,4-butanediol free radicals, preferred polyalkylene terephthalate esters may comprise up to 20 mole % of from 3 to 12 carbon atoms. Other aliphatic diols or cycloaliphatic diols having 6 to 21 carbon atoms, such as 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentane Glycol, 1,6-hexanediol, cyclohexane-1,4-dimethanol, 3-methyl-2,4-pentanediol, 2-methyl-2,4-pentanediol, 2, 2,4-trimethyl-1,3-pentanediol and 2-ethyl-1,6-hexanediol, 2,2-diethyl-1,3-propanediol, 2,5-hexanediol , 1,4-bis-(β-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-1,1,3,3-tetra Free radicals of methyl-cyclobutane, 2,2-bis-(3-β-hydroxyethoxyphenyl)-propane and 2,2-bis-(4-hydroxypropoxyphenyl)-propane ( DE-A 24 07 674, 24 07 776, 27 15 932).

The poly(p-alkyl phthalate) may be, for example, branched via a relatively small amount of a trihydric or tetrahydric alcohol or a combination of a tribasic carboxylic acid or a tetrabasic carboxylic acid, for example according to DE -A 1 900 270 and US-PS 3 692 744. Examples of preferred branching agents include 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, trimethylolethane, trimethylolpropane, and pentaerythritol.

In certain embodiments, particularly preferred are the soles of self-p-citric acid and its reactive derivatives (eg, dialkyl esters thereof) with ethylene glycol and/or 1,4- A mixture of polyalkylene terephthalate esters prepared from butanediol, and such polyalkylene terephthalate alkyl esters.

The mixture of poly(p-alkyl phthalate) preferably comprises from 1 to 50 wt.% (preferably from 1 to 30 wt.%) of polyethylene terephthalate and from 50 to 99 wt.% (preferably 70 to 99 wt.%) of polybutylene terephthalate.

The preferred polyalkylene terephthalate esters are typically used in phenol/o-dichlorobenzene (1:1 parts by weight) at a temperature of 25 ° C in an Ubbelohde viscometer of 0.4 to 1.5 deciliters per gram ( Dl/g), preferably a limiting viscosity of from 0.5 to 1.2 deciliters per gram.

Such poly(p-alkyl phthalate) esters can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695ff, Carl-Hanser-Verlag, Munich 1973).

Ingredient E

The composition may optionally further comprise one or more commercially available additives according to ingredient E, such as a lubricant, a release agent (eg, neopentyltetrastearate), a nucleating agent, a stabilizer, antistatic Agents (such as conductive carbon black, carbon fiber, carbon nanotubes and organic antistatic agents such as polyalkylene ethers, alkyl sulfonates or polymers containing polyamines), acids, fillers and reinforcement Materials such as glass or carbon fiber, mica, kaolin, talc, CaCO ₃ and glass flakes, as well as colorants and pigments. Other additives known in the art or other known sources may also be included if desired for any reason.

mold Preparation of composition and molded article

The thermoplastic molding composition can be, for example, by mixing the individual components and melting the demodulation in a known manner, and at a temperature of from 220 ° C to 320 ° C (preferably from 240 ° C to 300 ° C) to an existing device (such as It is prepared by melt-extruding the mixture in an internal kneader, an extruder, and a twin-shaft screw.

The mixing of the individual ingredients can be carried out in a known manner, i.e., continuously or simultaneously, at about 20 ° C (room temperature) or at a higher temperature.

There is also provided a method for preparing a molded composition and the use of the molded composition in the manufacture of a molded article, and the molded article itself.

These molding compositions can be used in the manufacture of molded articles of any kind. These can be manufactured by injection molding, extrusion, and blow molding methods. Another form of processing is the manufacture of molded articles via deep-drawing from previously fabricated panels or films.

Examples of such molded articles are films, profiles, cast parts of any kind (for example for household appliances such as televisions, juicers, coffee machines, mixers; for office equipment such as displays, flat screens, notes) Computers, printers, copiers, sheets, tubes, conduits for electrical installations, windows, doors and other profiles for the construction sector (internal assembly and external use) and parts for electronics and electrical engineering (such as switches, plugs and sockets), as well as body and internal components for commercial vehicles (specifically for the automotive sector).

In particular, molding compositions can also be used, for example, in the manufacture of molded articles or molded articles: for internal finishing parts of railway vehicles, boats, airplanes, buses, and other motor vehicles. , an outer casing for an electric device including a small voltage device, a casing for a device for distributing and transmitting information, a casing and a covering for a medical device, a massage device and a casing thereof, a toy vehicle for children, a prefabricated wall Boards for security devices and enclosures for televisions, thermal insulation transport containers, mouldings for sanitary and bathroom fittings, covering grids for ventilator openings, and enclosures for gardening equipment.

The following examples serve to further illustrate the invention.

Instance Ingredient A

An unbranched polycarbonate having a relative solution viscosity of η _rel = 1.28 (measured in CH ₂ Cl ₂ as a solvent at 25 ° C and a concentration of 0.5 g / 100 ml) based on bisphenol A.

Component B-1

Impact modifier, the following graft polymer

B-1.1 11 wt.% of methyl methacrylate grafted onto the following

B-1.2 89wt.% of a neodymium-acrylate composite rubber as a graft base, the helium-oxygen acrylate rubber comprises

B-1.2.1 92wt.% of silicone rubber and

B-1.2.2 8wt.% polybutyl acrylate rubber, and

The two mentioned rubber components B-1.2.1 and B-1.2.2 interpenetrate in the composite rubber so that they are substantially inseparable from each other.

Ingredient B-2

Impact modifier, the following graft polymer

B-2.1 17 wt.% of methyl methacrylate grafted onto the following

B-2.2 83wt.% of a neodymium-acrylate composite rubber as a graft base, the helium-oxygen acrylate rubber comprises

B-2.2.1 11wt.% of silicone rubber and

B-2.2.2 89wt.% polybutyl acrylate rubber, and

The two mentioned rubber components B-2.2.1 and B-2.2.2 interpenetrate in the composite rubber so that they are substantially inseparable from each other.

Component C-1

In the presence of a polybutadiene-styrene block copolymer rubber having an acrylonitrile-butadiene-styrene terpolymer of 18 wt.% of a styrene content of 26 wt.%, via propylene Preparation of acrylonitrile-butadiene-styrene by a total polymerization of 82 wt.% of a mixture of 24 wt.% of acrylonitrile and 76 wt.% of styrene based on nitrile-butadiene-styrene terpolymer Terpolymer. The weight average molecular weight M _w of the free styrene-acrylonitrile (SAN) copolymer component in the acrylonitrile-butadiene-styrene terpolymer is 80,000 g/mole (by gel permeation chromatography) Measured in tetrahydrofuran (THF)). The gel content of the acrylonitrile-butadiene-styrene terpolymer was 24 wt.% (measured in acetone).

Ingredient C-2

An acrylonitrile-butadiene-styrene terpolymer was prepared via bulk polymerization in which the weight ratio of acrylonitrile:butadiene:styrene was 20:16:64. The weight average molecular weight M _w of the free styrene-acrylonitrile copolymer component in the acrylonitrile-butadiene-styrene terpolymer is 168,000 g/mole (measured by gel permeation chromatography in tetrahydrofuran) ). The gel content of the acrylonitrile-butadiene-styrene terpolymer was 30 wt.% (measured in acetone).

Ingredient D

A copolymer of 77 wt.% of acrylonitrile and 23 wt.% of styrene having a weight average molecular weight M _{w of} 130 kg/mol (determined by gel permeation chromatography) was prepared via bulk polymerization.

Ingredient E

Ingredient E-1: Pentaerythritol tetrastearate component E-2: B900 (manufacturer: Ciba Specialty Chemicals Inc., Basel, Switzerland)

Preparation and testing of molding compositions

The individual substances listed in Table 1-2 are at a rate of 225 rpm and a throughput of 20 kg/hr at a machine temperature of 260 ° C in a twin-screw extruder (ZSK-25) ( Werner und Pfleiderer) is formulated and then granulated.

The finished granules were processed into a corresponding test sample in an injection molding machine (melting temperature 260 ° C, tool temperature 80 ° C, flow front speed 240 mm / sec). According to DIN EN ISO 527 (elongation at break, determined by tensile test), ISO 11443 (melting viscosity at 260 ° C and shear rate of 1,000 sec ^-1 (s ^-1 )), and DIN EN ISO 1133 (in The melt volume flow rate (MVR) at 260 ° C and the cube load of 5 kg are described as properties.

The change in MVR was measured using a load of 5 kg according to ISO 1133 at 260 ° C for a load of 5 kg at 95 ° C and 100% relative humidity ("FWL storage") as a hydrolysis of the prepared composition. Stability measure. Comparing the MVR values before storage, the increase in MVR value is measured by ΔMVR (hydrolysis), which is defined by the following formula:

The compositions of Examples 1 and 3 have higher hydrolysis stability, higher elongation at break, and lower melt viscosity than the compositions of the comparative examples, which is clear from Table 1.

Acrylonitrile-butadiene-styrene terpolymer C-2 comprises a copolymer of free state, ie a copolymer which is not chemically bonded to rubber, and has a ratio of acrylonitrile-butadiene-styrene terpolymer C -1 is the high quality of the ear. The composition comprising the component C-1 (Examples 5 and 7 ) has higher hydrolysis stability, higher elongation at break and lower melting than the composition of Comparative Examples 6 and 8 containing the component C-2. Viscosity.

It will be apparent that many modifications, substitutions and variations are possible in the present invention. It will be appreciated that specific embodiments may be practiced otherwise than as specifically described. Such modifications, substitutions and variations are intended to be included within the scope of this patent application. The articles such as "a", "the", "the"

Claims (20)

A composition comprising: A) 40 to 99 parts by weight of an aromatic polycarbonate and/or an aromatic polyester carbonate, in each case, by weight of the component A+B+C, B) In each case, 0.5 to 20 parts by weight of the first graft polymer, based on the sum of the parts by weight of the component A+B+C, wherein the graft base is a silicone rubber and a poly(meth)acrylic acid alkyl group. An oxirane-acrylate composite rubber of an ester rubber, wherein the oxime rubber is present in an amount of 65 to 95 wt.% based on the graft base, and C) is in each case a weight of the component A+B+C One part of 0.5 to 40 parts by weight of the second graft polymer comprising a copolymer which is not chemically bonded to the rubber and has a weight average molecular weight of 60,000 to 150,000 g/mole, wherein the composition does not contain Fire retardant. The composition of claim 1, which comprises the following graft polymer as component B: B.15 to 95 wt.% of a vinyl monomer B.2 grafted to one or more of the following 95 to 5 wt.% of one or more oxirane-acrylate composite rubbers as a graft base, wherein the oxime-acrylate rubber comprises B.2.1 65 to 95 wt.% of oxime rubber and B.2.2 35 to 5 wt.% of polyalkyl (meth) acrylate rubber, wherein the two mentioned rubber components B.2.1 and B.2.2 The mutual penetration of the composite rubber causes B.2.2 and B.2.2 to be substantially inseparable from each other. The composition of claim 2, wherein the vinyl monomer B.1 is at least one group consisting of styrene, α-methylstyrene, methyl methacrylate, n-butyl acrylate and acrylonitrile. Selected in the middle. A composition according to claim 1 which comprises a graft polymer of the following C as a component C: C. 1) 5 to 95 wt.% of a mixture C of the following component C.1.1). 1 to 65 to 85 wt.% of at least one of a vinyl type aromatic compound, a ring-substituted vinyl type aromatic compound, and a (C ₁ -C ₈ )-alkyl methacrylate group The monomer selected from the group, and C.1.2) at least one of 15 to 35 wt.% of C.1 is composed of a vinyl type cyanide or a (C ₁ -C ₈ )-alkyl ester (meth)acrylate. And a monomer selected from the group consisting of derivatives of unsaturated carboxylic acids, and grafted on at least one of the following C. 2) 95 to 5 wt.% of a graft having a glass transition temperature of <0 ° C, The graft base C.2) has an average particle size of 0.05 to 10 microns, a d ₅₀ value. The composition of claim 4, wherein the graft base C.2 is composed of a diene rubber, a diene-vinyl block copolymer rubber, an ethylene/propylene rubber, an ethylene/propylene/diene. It is selected from the group consisting of rubber, acrylate, polyurethane, oxime, chloroform and ethylene/vinyl acetate rubber, and the limitation is that it does not include a mixture of oxime rubber and acrylate rubber. A composition according to claim 1 which comprises a copolymer which is not chemically bonded to rubber and has a weight average molecular weight of 70,000 to 90,000 g/mol as component C. The composition of claim 4, which comprises a method prepared by a bulk, solution and/or bulk-suspension polymerization method and having a rubber content, that is, the content of component C.2 in the graft polymer C is 10 a graft polymer of up to 20 wt.%, and a graft shell as component C, the graft shell comprising, in each case, at least one of 20 to 30 wt.%, based on the monomer of the graft shell, according to C. 1.2 monomers, and 70 to 80 wt.% of at least one monomer according to C.1.1. The composition of claim 1 which comprises, by weight of the component A+B+C+D, at least one of 3 to 16 parts by weight of the rubber-free vinyl (co)polymer and A polymer selected from the group consisting of polyparaphenylene alkyl esters as component D. Such as the composition of claim 1 of the scope of the patent, which contains The sum of the parts by weight of A+B+C+D, at least one of 3 to 16 parts by weight consists of a rubber-free vinyl (co)polymer D.1 and a poly(p-alkylene terephthalate D.2). The selected polymer from the group is used as component D. The composition of claim 1, which comprises, in each case, 0 to 50 parts by weight of at least one of a lubricant, a releasing agent, and a crystal nucleus, based on the sum of the parts by weight of the component A+B+C. An additive selected from the group consisting of a forming agent, a stabilizer, an antistatic agent, an acid, a filler, a reinforcing material, a colorant, and a pigment. A composition consisting of: A) 40 to 99 parts by weight of an aromatic polycarbonate and/or an aromatic polymer, in each case, by weight of the component A+B+C+D The ester carbonate, B) in each case, 0.5 to 20 parts by weight of the first graft polymer, based on the sum of the parts by weight of the component A+B+C+D, wherein the graft base is infiltrated with each other An oxygen-acrylate composite rubber of an oxy-rubber and a polyalkyl (meth) acrylate rubber, wherein the amount of the oxirane rubber is 65 to 95 wt.% based on the graft base, and C) is the component A+B+ One to 0.5 to 20 parts by weight of the sum of parts by weight of C + D comprising a copolymer non-chemically bonded to rubber, and a second graft polymer having a weight average molecular weight of 60,000 to 150,000 g/mole, D) 3 to 16 by weight of the components A+B+C+D At least one selected from the group consisting of rubber-free vinyl (co)polymers and polyalkylene terephthalate, and E) optionally 0.5 to 25 parts by weight (in each case) In the case of at least one additive based on the sum of the weight fractions of the components A+B+C+D, selected from the group consisting of lubricants, mold release agents, nucleating agents, stabilizers, antistatic agents, acids, fillers , a group of reinforcing materials, colorants and pigments. The composition of claim 11 wherein the amount of the component B is 8 to 13 parts by weight based on the sum of the parts by weight of the component A+B+C+D, and the amount of the component C is the component A+B. The sum of the parts by weight of +C+D is 7 to 16 parts by weight. For example, the composition of claim 11 is composed of A, B, C, and D. For example, the composition of claim 11 is composed of A, B, C, D and E. A molded article comprising the composition of claim 1 of the patent application. A molded article comprising the composition of claim 11 of the patent application. A molded article of claim 16, wherein the molded article is a motor vehicle, a railway vehicle, an aircraft, a ship component, a film, a profile, and/or any type of outer casing component. A method for preparing a molded article according to claim 15 which comprises mixing A, B, C and D to form a mixture, and melt-demodulating and melt-extruding the mixture. The method of claim 18, wherein the method is carried out at a temperature of from 220 ° C to 320 ° C. The method of claim 18, wherein the method is carried out using an internal kneader, an extruder, and/or a biaxial helix.